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C−H Activation by an Iron‐Nitrido Bis‐Pocket Porphyrin Species
Author(s) -
Wang HaiXu,
Wu Liangliang,
Zheng Bin,
Du Lili,
To WaiPong,
Ko ChengHoi,
Phillips David Lee,
Che ChiMing
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202014191
Subject(s) - chemistry , porphyrin , protonation , flash photolysis , photochemistry , photodissociation , ligand (biochemistry) , dissociation (chemistry) , reagent , reactivity (psychology) , medicinal chemistry , reaction rate constant , bond cleavage , inorganic chemistry , kinetics , catalysis , organic chemistry , medicine , ion , biochemistry , physics , receptor , alternative medicine , quantum mechanics , pathology
High‐valent iron‐nitrido species are nitrogen analogues of iron‐oxo species which are versatile reagents for C−H oxidation. Nonetheless, C−H activation by iron‐nitrido species has been scarcely explored, as this is often hampered by their instability and short lifetime in solutions. Herein, the hydrogen atom transfer (HAT) reactivity of an Fe porphyrin nitrido species ( 2 c ) toward C−H substrates was studied in solutions at room temperature, which was achieved by nanosecond laser flash photolysis (LFP) of its Fe III ‐azido precursor ( 1 c ) supported by a bulky bis‐pocket porphyrin ligand. C−H bonds with bond dissociation enthalpies (BDEs) of up to ≈84 kcal mol −1 could be activated, and the second‐order rate constants ( k 2 ) are on the order of 10 2 –10 4 s −1 m −1 . The Fe‐amido product formed after HAT could further release ammonia upon protonation.